US20190309207A1 - Resin Composition - Google Patents
Resin Composition Download PDFInfo
- Publication number
- US20190309207A1 US20190309207A1 US16/470,415 US201816470415A US2019309207A1 US 20190309207 A1 US20190309207 A1 US 20190309207A1 US 201816470415 A US201816470415 A US 201816470415A US 2019309207 A1 US2019309207 A1 US 2019309207A1
- Authority
- US
- United States
- Prior art keywords
- resin composition
- thermally conductive
- filler
- particle diameter
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- QJYGMJFOIUTUSV-UHFFFAOYSA-H O=C(CCCCCO)O[Y]OC(=O)CCCCCO.[H]O[Y]OC(=O)CC(=O)O[Y]O Chemical compound O=C(CCCCCO)O[Y]OC(=O)CCCCCO.[H]O[Y]OC(=O)CC(=O)O[Y]O QJYGMJFOIUTUSV-UHFFFAOYSA-H 0.000 description 2
- DPGYQCZNRITNSM-UHFFFAOYSA-L O=C(CCCCCO)O[Y]OC(=O)CCCCCO Chemical compound O=C(CCCCCO)O[Y]OC(=O)CCCCCO DPGYQCZNRITNSM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
Definitions
- the present application relates to a resin composition.
- the present application relates to a resin composition. It is an object of the present application to provide a resin composition which is capable of forming a resin satisfying required physical properties such as thermal conductivity and insulation properties and has excellent handling properties such as viscosity and thixotropy.
- the physical properties are physical properties measured at room temperature, unless otherwise specified.
- room temperature is a natural temperature without being heated or cooled, which may be, for example, any temperature in a range of 10° C. to 30° C., or a temperature of about 23° C. or about 25° C. or so.
- the present application relates to a resin composition.
- the resin composition may comprise a resin component and thermally conductive fillers.
- the resin composition may be an adhesive composition, that is, an adhesive as such, or a composition capable of forming an adhesive through a reaction such as a curing reaction.
- a resin composition may be a solvent resin composition, a water-based resin composition, or a solventless resin composition.
- the resin composition can be prepared by adding thermally conductive fillers to be described below to a resin composition capable of forming a known acrylic adhesive, epoxy adhesive, urethane adhesive, olefin adhesive, EVA (ethylene vinyl acetate) adhesive or silicone adhesive.
- the range of the term resin component includes components that can be converted into resins through a curing reaction or a polymerization reaction as well as components that are generally known as resins.
- an adhesive resin or a precursor capable of forming an adhesive resin can be applied as the resin component.
- An example of such a resin component includes an acrylic resin, an epoxy resin, a urethane resin, an olefin resin, an EVA (ethylene vinyl acetate) resin or a silicone resin, and the like, or a precursor such as polyol or an isocyanate compound, and the like, but is not limited thereto.
- the resin composition of the present application may be a one-component resin composition or a two-component resin composition.
- the two-component resin composition is separated into a principal agent composition and a curing agent composition, as known in the art, and the two separated compositions are mixed and reacted to be capable of forming a resin, where when the resin composition of the present application is a two-component type, the resin composition containing the resin component and the fillers may be the principal agent composition, the curing agent composition or a mixture thereof, or may refer to a state after they have been mixed and reacted.
- the resin composition may be a urethane resin composition, and may be a two-component urethane resin composition.
- the term two-component urethane resin composition is a composition capable of forming a resin by blending a principal agent composition and a curing agent composition, where the polyurethane can be formed by the reaction of the principal agent and the curing agent.
- the resin composition of the present application may be a principal agent composition of a two-component urethane resin composition, a curing agent composition of a two-component urethane resin composition or a mixture of the principal agent and curing agent compositions, or may refer to a mixture in which the resin has been formed by the urethane reaction in the mixture.
- the principal agent composition of the two-component urethane-based resin composition may comprise at least polyol, and the curing agent composition may comprise an isocyanate compound such as polyisocyanate.
- the urethane resin that is, the polyurethane formed by the reaction of the two-component urethane resin composition may comprise at least a polyol-derived unit and a polyisocyanate-derived unit.
- the polyol-derived unit may be a unit in which the polyol is formed by a urethane reaction with the polyisocyanate
- the polyisocyanate-derived unit may be a unit in which the polyisocyanate is formed by a urethane reaction with the polyol.
- a resin composition comprising polyol which is amorphous or has sufficiently low crystallinity may be applied.
- amorphous means a case where a crystallization temperature (Tc) and a melting temperature (Tm) are not observed in the following DSC (differential scanning calorimetry) analysis.
- the DSC analysis can be performed in a range of ⁇ 80° C. to 60° C. at a rate of 10° C./minute, which can be measured, for example, by a method of raising the temperature from 25° C. to 60° C. at the above rate, lowering it to ⁇ 80° C. again and raising it to 60° C. again.
- the sufficiently low crystallinity herein means a case where the melting point (Tm) observed in the DSC analysis is about 20° C. or lower, about 15° C.
- the melting point is not particularly limited, and for example, the melting point may be about ⁇ 80° C. or higher, about ⁇ 75° C. or higher, or about ⁇ 70° C. or higher.
- an ester-based polyol to be described below can be exemplified. That is, among the ester-based polyols, a carboxylic acid-based polyol or a caprolactone-based polyol, specifically polyol having a structure to be described below, effectively satisfies the above-mentioned characteristics.
- the carboxylic acid-based polyol is formed by a urethane reaction of a component comprising dicarboxylic acid and polyol (ex. diol or triol), and the caprolactone-based polyol is formed by reacting caprolactone and polyol (ex. diol or triol), where the polyol satisfying the above-described physical properties can be constituted through control of the kind and ratio of each component.
- the polyol may be polyol represented by Formula 1 or 2 below.
- X is a dicarboxylic acid-derived unit
- Y is a polyol-derived unit, for example, a triol or diol unit
- n and m are arbitrary numbers.
- the dicarboxylic acid-derived unit is a unit formed by a urethane reaction of dicarboxylic acid with polyol
- the polyol-derived unit is a unit formed by a urethane reaction of polyol with dicarboxylic acid or caprolactone.
- Y in Formula 2 also represents a moiety excluding the ester bond.
- the polyol-derived unit of Y herein is a unit derived from polyol containing three or more hydroxyl groups such as a triol unit, a structure in which the Y moiety is branched in the structure of the above formula may be realized.
- the kind of the dicarboxylic acid-derived unit of X in Formula 1 is not particularly limited, but it may be any one unit selected from the group consisting of a phthalic acid unit, an isophthalic acid unit, a terephthalic acid unit, a trimellitic acid unit, a tetrahydrophthalic acid unit, a hexahydrophthalic acid unit, a tetrachlorophthalic acid unit, an oxalic acid unit, an adipic acid unit, an azelaic acid unit, a sebacic acid unit, a succinic acid unit, a malic acid unit, a glutaric acid unit, a malonic acid unit, a pimelic acid unit, a suberic acid unit, a 2,2-dimethylsuccinic acid unit, a 3,3-dimethylglutaric acid unit, a 2,2-dimethylglutaric acid unit, a maleic acid unit, a fumaric acid unit, an itaconic acid
- the kind of the polyol-derived unit of Y is not particularly limited, but it may be any one or two or more selected from the group consisting of an ethylene glycol unit, a propylene glycol unit, an 1,2-butylene glycol unit, a 2,3-butylene glycol unit, an 1,3-propanediol unit, an 1,3-butanediol unit, an 1,4-butanediol unit, an 1,6-hexanediol unit, a neopentyl glycol unit, an 1,2-ethylhexyldiol unit, an 1,5-pentanediol unit, an 1,10-decanediol unit, an 1,3-cyclohexanedimethanol unit, an 1,4-cyclohexanedimethanol unit, a glycerin unit and a trimethylol propane unit for securing units and desired physical properties.
- n is an arbitrary number, and the range may be selected in consideration of desired physical properties, and may be, for example, about 2 to 10 or 2 to 5.
- m is an arbitrary number, and the range may be selected in consideration of desired physical properties, and may be, for example, about 1 to 10 or 1 to 5.
- the molecular weight of this polyol may be adjusted in consideration of desired low viscosity characteristics, durability or adhesiveness, and the like, which may be, for example, in a range of about 300 to 2,000.
- the molecular weight mentioned in this specification may be, for example, a weight average molecular weight measured by using GPC (gel permeation chromatograph), and unless otherwise specified herein, the molecular weight of a polymer means a weight average molecular weight.
- the kind of the polyisocyanate contained in the curing agent composition of the two-component urethane-based resin composition is not particularly limited, but it may be advantageous that it is an alicyclic series in order to secure desired physical properties.
- the term polyisocyanate may mean a multifunctional isocyanate compound containing at least two isocyanate groups.
- the polyisocyanate may be an aromatic polyisocyanate compound such as tolylene diisocyanate, diphenylmethane diisocyanate, phenylenediisocyanate, polyethylenephenylene polyisocyanate, xylene diisocyanate, tetramethylxylylene diisocyanate, trizine diisocyanate, naphthalene diisocyanate and triphenylmethane triisocyanate, an aliphatic polyisocyanate such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate methyl, ethylene diisocyanate, propylene diisocyanate or tetramethylene diisocyanate, or an alicyclic polyisocyanate such as transcyclohexane-1,4-diisocyanate, isoboron diisocyanate, bis(isocyanate
- the ratio of the polyol to the polyisocyanate in the resin composition is not particularly limited and is appropriately controlled so as to enable the urethane reaction thereof.
- the resin composition may comprise fillers together with the resin component.
- the fillers may be thermally conductive fillers.
- thermally conductive filler means a material known to have thermal conductivity of about 0.5 W/mK or more, about 1 W/mK or more, 1.5 W/mK or more, 2 W/mK or more, 2.5 W/mK or more, 3 W/mK or more, 4 W/mK or more, 4.5 W/mK or more, about 5 W/mK or more, 5.5 W/mK or more, 6 W/mK or more, 6.5 W/mK or more, 7 W/mK or more, 7.5 W/mK or more, 8 W/mK or more, 8.5 W/mK or more, 9 W/mK or more, 9.5 W/mK or more, 10 W/mK or more, 10.5 W/mK or more, 11 W/mK or more, 11.5 W/mK or more, 12 W/mK or more, 12.5 W/mK or more, 13 W/
- the thermal conductivity of the thermally conductive filler may be about 400 W/mK or less, about 350 W/mK or less, about 300 W/mK or less, about 250 W/mK or less, about 200 W/mK or less, about 150 W/mK or less, about 100 W/mK or less, about 90 W/mK or less, about 80 W/mK or less, about 70 W/mK or less, about 60 W/mK or less, about 50 W/mK or less, about 40 W/mK or less, about 30 W/mK or less, about 20 W/mK or less, or about 15 W/mK or less or so.
- thermally conductive fillers is not particularly limited, but ceramic fillers can be applied in consideration of insulation and the like.
- ceramic particles such as alumina, AlN (aluminum nitride), BN (boron nitride), silicon nitride, SiC or BeO may be used. If insulation properties can be secured, application of carbon fillers such as graphite may also be considered.
- the resin composition may comprise the thermally conductive fillers in an amount of about 600 parts by weight or more relative to 100 parts by weight of the resin component.
- the ratio of the fillers may be 650 parts by weight or more, or 700 parts by weight or more, relative to 100 parts by weight of the resin component.
- the ratio may be about 2,000 parts by weight or less, about 1,500 parts by weight or less, or about 1,100 parts by weight or less, relative to 100 parts by weight of the resin component. It is possible to secure desired physical properties such as thermal conductivity and insulation within the ratio range of the fillers.
- the ratio of the fillers in the resin composition mentioned in this specification may be a ratio of the resin component that is a principal agent of the principal agent composition, or a ratio of the curing agent that is a resin component of the curing agent composition, or may be a ratio of the final resin formed by the reaction of the principal agent and the curing agent.
- the viscosity of the resin composition is greatly increased and the handling property is accordingly deteriorated, and even after the resin material is formed, it contains bubbles or voids, whereby the thermal conductivity may be lowered.
- the resin composition at least three kinds of fillers having different particle diameters are applied at a predetermined ratio.
- the resin composition may comprise a first thermally conductive filler having a D50 particle diameter of 35 ⁇ m or more, a second thermally conductive filler having a D50 particle diameter in a range of 15 ⁇ m to 30 ⁇ m, and a third thermally conductive filler having a D50 particle diameter of 1 to 4 ⁇ m.
- the D50 particle diameter is a particle diameter (median diameter) at 50% of accumulation of particle size distribution on a volumetric basis, which means a particle diameter at the point where the cumulative value becomes 50% in the cumulative curve that the particle size distribution is obtained on a volumetric basis and the whole volume is set to 100%.
- a D50 particle diameter can be measured by a laser diffraction method.
- the D50 particle diameter of the first thermally conductive filler may be in a range of 35 to 80 ⁇ m or in a range of about 40 to 70 ⁇ m.
- the D50 particle diameter of the second thermally conductive filler may be in a range of 15 to 25 ⁇ m or in a range of about 20 to 25 ⁇ m.
- the D50 particle diameter of the third thermally conductive filler may be in a range of 1 to 3 ⁇ m or in a range of about 2 to 3 ⁇ m.
- the relationship of the D50 particle diameters in the respective thermally conductive fillers may be controlled, and for example, a ratio (A/B) of the D50 particle diameter (A) of the first thermally conductive filler to the D50 particle diameter (B) of the second thermally conductive filler may be in a range of 1.5 to 10, and a ratio (B/C) of the D50 particle diameter (B) of the second thermally conductive filler to the D50 particle diameter (C) of the third thermally conductive filler may be in a range of 8 to 15.
- the ratio (A/B) may be 2 or more, and may be 9 or less, 8 or less, 7 or less, 6 or less, or 5 or less.
- the ratio (B/C) may be 9 or more, or 10 or more, and may be 14 or less, 13 or less, or 12 or less.
- the resin composition may comprise 30 to 50 wt % or about 35 to 45 wt % of the first thermally conductive filler, and 25 to 45 wt %, about 25 to 40 wt % or about 30 to 45 wt % of the second thermally conductive filler, and may comprise 15 to 35 wt % or about 20 to 30 wt % of the third thermally conductive filler, when the total weight of the first to third thermally conductive fillers is 100 wt %.
- the shape of the filler is not particularly limited, which may be selected in consideration of the viscosity and thixotropy of the resin composition, the settling possibility in the composition, desired thermal resistance or thermal conductivity, insulation, a filling effect or dispersibility, and the like.
- a spherical filler in consideration of the amount to be filled, but in consideration of formation of a network, conductivity, thixotropy, etc., a non-spherical filler, for example, a filler having a shape such as a needle shape or a plate shape can also be used.
- the term spherical particle means a particle having sphericity of about 0.95 or more, and the non-spherical particle means a particle having sphericity of less than 0.95.
- the sphericity can be confirmed through particle shape analysis of particles, which can be measured by the method described in the examples to be described below.
- all the spherical fillers that is, fillers having sphericity of 0.95 or more may be used as the first to third thermally conductive fillers in consideration of the filling effect as described above.
- at least one of the first to third thermally conductive fillers may be a non-spherical filler having sphericity of less than 0.95.
- the composition may exhibit thixotropy.
- the resin composition may basically comprise the above components, that is, the resin component and the thermally conductive fillers, and may also comprise other components, if necessary.
- the resin composition may further comprise a viscosity control agent, such as a thixotropic agent, a diluent, a dispersing agent, a surface treatment agent or a coupling agent, for controlling viscosity, for example, for increasing or decreasing viscosity, or for controlling viscosity according to shear force.
- a viscosity control agent such as a thixotropic agent, a diluent, a dispersing agent, a surface treatment agent or a coupling agent, for controlling viscosity, for example, for increasing or decreasing viscosity, or for controlling viscosity according to shear force.
- the thixotropic agent can control the viscosity of the resin composition according to shear force, so that a process of manufacturing a battery module can be effectively performed.
- the usable thixotropic agent can be exemplified by fumed silica and the like.
- the diluent or dispersing agent is usually used for lowering the viscosity of the resin composition, and as long as it can exhibit the above action, a variety of shapes known in the art can be used without limitation.
- the surface treatment agent is used for surface treatment of the filler introduced into the resin composition, and as long as it can exhibit the above action, a variety of shapes known in the art can be used without limitation.
- the coupling agent may be used, for example, to improve the dispersibility of the thermally conductive fillers such as alumina, and as long as it can exhibit the above action, a variety of shapes known in the art can be used without limitation.
- the resin composition may further comprise a flame retardant or a flame retardant aid.
- a resin composition can form a flame retardant resin composition.
- various known flame retardants can be applied without particular limitation, and for example, solid phase filler-type flame retardants or liquid flame retardants and the like can be applied.
- the flame retardant includes an organic flame retardant such as melamine cyanurate or an inorganic flame retardant such as magnesium hydroxide, but is not limited thereto.
- a liquid type flame retardant material (TEP, triethyl phosphate or TCPP, tris(1,3-chloro-2-propyl)phosphate, etc.) may also be used.
- a silane coupling agent capable of acting as a flame retardant synergist may also be added.
- the resin composition may comprise any one or two or more of the above components.
- Such a resin composition can form a resin having excellent thermal conductivity and satisfying other required physical properties such as insulation.
- the resin composition may have thermal conductivity of about 2 W/mK or more, 2.5 W/mK or more, 3 W/mK or more, 3.5 W/mK or more, or 4 W/mK or more, or may form such a resin.
- the thermal conductivity may be 50 W/mK or less, 45 W/mK or less, 40 W/mK or less, 35 W/mK or less, 30 W/mK or less, 25 W/mK or less, 20 W/mK or less, 15 W/mK or less, 10 W/mK or less, 5 W/mK or less, 4.5 W/mK or less, or about 4.0 W/mK or less.
- the thermal conductivity may be, for example, a numerical value measured according to ASTM D5470 standard or ISO 22007-2 standard.
- the thermal conductivity can be secured by controlling the kind of the resin components used in the resin composition and the ratios of the thermally conductive fillers as described above, and the like.
- resin components known to be generally usable as adhesives it is known that an acrylic resin, a urethane resin and a silicone resin have similar heat conduction properties to each other, an epoxy resin has excellent thermal conductivity relative to these resins, and an olefin resin has higher thermal conductivity than the epoxy resin. Therefore, it is possible to select one having excellent thermal conductivity among the resins as necessary.
- the desired thermal conductivity cannot be secured with only the resin component, so that the thermal conductivity can be achieved by incorporating the filler component into the resin layer at a proper ratio.
- the resin composition may be an adhesive material, as described above, and may have adhesive force of about 50 gf/10 mm or more, about 70 gf/10 mm or more, about 80 gf/10 mm or more, or about 90 gf/10 mm or more, and about 1,000 gf/10 mm or less, about 950 gf/10 mm or less, about 900 gf/10 mm or less, about 850 gf/10 mm or less, about 800 gf/10 mm or less, about 750 gf/10 mm or less, about 700 gf/10 mm or less, about 650 gf/10 mm or less, or about 600 gf/10 mm or less, or may form a resin layer having this adhesive force.
- the adhesive force may be a value measured at a peeling speed of about 300 mm/min and a peeling angle of 180 degrees.
- the adhesive force may be an adhesive force to aluminum.
- the resin composition is an electrically insulating resin composition, which may have an insulation breakdown voltage of about 3 kV/mm or more, about 5 kV/mm or more, about 7 kV/mm or more, 10 kV/mm or more, 15 kV/mm or more, or 20 kV/mm or more, as measured based on ASTM D149, or may form such a resin layer.
- Such an insulation breakdown voltage can also be controlled by controlling the insulation of the resin component or the type of the filler, and the like.
- the ceramic filler is known as a component that can secure insulation.
- the resin composition may be a flame retardant resin composition.
- flame retardant resin composition may mean a resin composition showing a V-0 rating in UL 94 V Test (vertical burning test) or a resin composition capable of forming such a resin.
- the resin composition also has a low shrinkage ratio during curing or after curing. Through this, it is possible to prevent the occurrence of peeling or voids, and the like that may occur during manufacturing or use processes.
- the shrinkage ratio can be appropriately adjusted within a range capable of exhibiting the above-described effect, which may be, for example, less than 5%, less than 3%, or less than about 1%. The lower the value of the shrinkage ratio is, the more advantageous it is, and thus the lower limit is not particularly limited.
- the resin composition also has a low coefficient of thermal expansion (CTE).
- CTE coefficient of thermal expansion
- the coefficient of thermal expansion can be appropriately adjusted within a range capable of exhibiting the above-described effect, which may be, for example, less than 300 ppm/K, less than 250 ppm/K, less than 200 ppm/K, less than 150 ppm/K, or less than about 100 ppm/K.
- the resin composition may also exhibit an appropriate viscosity by comprising the above components.
- the resin composition may have a viscosity at room temperature (frequency: 10 Hz) in a range of 50 Pas to 500 Pas.
- Such a resin composition may exhibit excellent physical properties such as excellent handling properties, processability and high thermal conductivity, thereby being used effectively as a heat dissipation material or a heat conduction material in various devices or instruments, and the like, including batteries, televisions, videos, computers, medical instruments, office machines or communication devices, and the like.
- the present application can provide a thermally conductive resin composition exhibiting high thermal conductivity while having excellent handling properties.
- the thermally conductive resin composition can be kept excellent in all other physical properties such as insulation.
- transmittance-variable device of the present application will be described in detail by way of examples and comparative examples, but the scope of the present application is not limited by the following transmittance-variable device.
- the thermal conductivity of the resin composition was measured according to ASTM D5470 standard. After a resin layer formed using a resin composition was placed between two copper bars, one of the two copper bars was brought into contact with a heater and the other was brought into contact with a cooler, and then a thermal equilibrium state (a state of showing a temperature change of about 0.1° C. or less for 5 minutes) was made by adjusting the capacity of the cooler while keeping the heater at a constant temperature, according to ASTM D5470 standard.
- the temperature of each copper bar was measured in the thermal equilibrium state, and the thermal conductivity (K, unit: W/mK) was evaluated according to the following equation.
- the pressure applied to the resin layer was adjusted to be about 11 Kg/25 cm 2 , and when the thickness of the resin layer was changed during the measurement, the thermal conductivity was calculated based on the final thickness.
- K thermal conductivity (W/mK)
- Q heat (unit: W) transferred per unit time
- dx is the thickness of the resin layer (unit: m)
- A is the cross-sectional area (unit: m 2 ) of the resin layer
- dT is the temperature difference (unit: K) between the copper bars.
- the D50 particle diameter of the filler was measured with a MASTERSIZER3000 instrument from Marvern Inc., based on ISO-13320 standard. Ethanol was used as a solvent upon the measurement.
- the incident laser is scattered by the particles dispersed in the solvent, and the intensity and the directional value of the scattered laser vary depending on the size of the particles, which are analyzed using the Mie theory.
- the particle diameter can be evaluated by obtaining the distribution through conversion to the diameter of a sphere having the same volume as that of the dispersed particle and obtaining the D50 value as the median value of the distribution through that.
- the sphericity of the filler as a three-dimensional particle is defined as the ratio (S′/S) of the surface area (S′) of the sphere having the same volume as the particle to the surface area (S) of the particle, which is usually an average value of circularity for the actual particles.
- the circularity is a ratio of a boundary of a circle having the same area (A) as the image obtained from the two-dimensional image of the particle to the boundary (P) of the image, theoretically being obtained by the following equation and a value from 0 to 1, and the circularity is 1 for an ideal circle.
- Circularity 4 ⁇ A/P 2 ⁇ Circularity Equation>
- the sphericity value is an average value of the circularity measured by a particle shape analysis instrument (FPIA-3000) from Marvern Inc.
- the viscosity of the resin composition was measured in a frequency sweep mode at 25° C. for the section from 0.1 to 100 Hz, after equipping an ARES-G2 instrument from TA Company with 8 mm parallel plates and then positioning the composition between the plates so as not to flow down, and the values at 10 Hz were described in Table 1.
- a resin composition As a resin composition, a two-component urethane-based adhesive composition was prepared.
- a principal agent composition comprising, as a caprolactone-based polyol of Formula A below, the polyol having m of Formula A below, as a number of repeated units, in a range of about 1 to 3 and containing an ethylene glycol and propylene glycol-derived unit as Y of Formula A below being a polyol-derived unit, was used as a principal agent composition, and a composition comprising polyisocyanate (HDI, hexamethylene diisocyanate) was used as a curing agent composition.
- Alumina was compounded to the resin composition so as to be capable of exhibiting thermal conductivity.
- the alumina was compounded to each of the principal agent composition and the curing agent composition by bisecting about 1,000 parts by weight of alumina by the same amount relative to 100 parts by weight of the polyurethane formed after the curing of the two-component urethane-based adhesive composition.
- alumina (first filler) having a D50 particle diameter of about 40 ⁇ m, alumina (second filler) having a D50 particle diameter of about 20 ⁇ m and alumina (third filler) having a D50 particle diameter of about 2 ⁇ m were used, and about 400 parts by weight of the first filler, about 300 parts by weight of the second filler and about 300 parts by weight of the third filler were applied, relative to 100 parts by weight of the polyurethane.
- first to third fillers all spherical fillers having a sphericity of 0.95 or more were used.
- the resin composition was prepared by adjusting equivalent amounts of the principal agent composition and the curing agent composition of the two-component composition and compounding them.
- a resin composition was prepared in the same matter as in Example 1, except that about 400 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 70 ⁇ m, about 300 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 ⁇ m and about 300 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- alumina first filler, spherical filler having sphericity of 0.95 or more
- second filler, spherical filler having sphericity of 0.95 or more having a D50 particle diameter of about 20 ⁇ m
- a resin composition was prepared in the same matter as in Example 1, except that about 400 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 ⁇ m, about 400 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 ⁇ m and about 200 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- alumina first filler, spherical filler having sphericity of 0.95 or more
- second filler, spherical filler having sphericity of 0.95 or more having a D50 particle diameter of about 20 ⁇ m
- a resin composition was prepared in the same matter as in Example 1, except that about 350 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 ⁇ m, about 350 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 ⁇ m and about 300 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- a resin composition was prepared in the same matter as in Example 1, except that about 450 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 ⁇ m, about 350 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 ⁇ m and about 200 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- alumina first filler, spherical filler having sphericity of 0.95 or more
- second filler, spherical filler having sphericity of 0.95 or more having a D50 particle diameter of about 20 ⁇ m
- a resin composition was prepared in the same matter as in Example 1, except that about 400 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 ⁇ m, about 300 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 ⁇ m and about 300 parts by weight of alumina (third filler, non-spherical filler having sphericity of less than 0.95) having a D50 particle diameter of about 2 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- alumina first filler, spherical filler having sphericity of 0.95 or more
- second filler spherical filler having sphericity of 0.95 or more
- a resin composition was prepared in the same matter as in Example 1, except that about 400 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 70 ⁇ m, about 300 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 ⁇ m and about 300 parts by weight of alumina (third filler, non-spherical filler having sphericity of less than 0.95) having a D50 particle diameter of about 2 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- alumina first filler, spherical filler having sphericity of 0.95 or more
- second filler, spherical filler having sphericity of 0.95 or more having a D50 particle diameter of about 20 ⁇ m
- a resin composition was prepared in the same matter as in Example 1, except that about 630 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 ⁇ m and about 270 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- first filler spherical filler having sphericity of 0.95 or more
- second filler, spherical filler having sphericity of 0.95 or more having a D50 particle diameter of about 20 ⁇ m
- a resin composition was prepared in the same matter as in Example 1, except that about 630 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 ⁇ m and about 270 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- first filler spherical filler having sphericity of 0.95 or more
- second filler, spherical filler having sphericity of 0.95 or more having a D50 particle diameter of about 2 ⁇ m
- a resin composition was prepared in the same matter as in Example 1, except that about 630 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 ⁇ m and about 270 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- first filler spherical filler having sphericity of 0.95 or more
- second filler, spherical filler having sphericity of 0.95 or more having a D50 particle diameter of about 2 ⁇ m
- a resin composition was prepared in the same matter as in Example 1, except that about 400 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 ⁇ m, about 300 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 5 ⁇ m and about 300 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- alumina first filler, spherical filler having sphericity of 0.95 or more
- second filler, spherical filler having sphericity of 0.95 or more having a D50 particle diameter of about 5 ⁇ m
- a resin composition was prepared in the same matter as in Example 1, except that about 400 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 ⁇ m, about 300 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 10 ⁇ m and about 300 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- alumina first filler, spherical filler having sphericity of 0.95 or more
- second filler, spherical filler having sphericity of 0.95 or more having a D50 particle diameter of about 10 ⁇ m
- a resin composition was prepared in the same matter as in Example 1, except that about 400 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 ⁇ m, about 300 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 ⁇ m and about 300 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 5 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- alumina first filler, spherical filler having sphericity of 0.95 or more
- second filler spherical filler having sphericity of 0.95 or more
- a resin composition was prepared in the same matter as in Example 1, except that about 400 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 ⁇ m, about 300 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 ⁇ m and about 300 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 0.5 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- alumina first filler, spherical filler having sphericity of 0.95 or more
- second filler spherical filler having sphericity of 0.95 or more
- a resin composition was prepared in the same matter as in Example 1, except that about 300 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 ⁇ m, about 300 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 ⁇ m and about 300 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- a resin composition was prepared in the same matter as in Example 1, except that about 300 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 ⁇ m, about 500 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 ⁇ m and about 200 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- alumina first filler, spherical filler having sphericity of 0.95 or more
- second filler, spherical filler having sphericity of 0.95 or more having a D50 particle diameter of about 20 ⁇ m
- a resin composition was prepared in the same matter as in Example 1, except that about 500 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 ⁇ m, about 200 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 ⁇ m and about 300 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- alumina first filler, spherical filler having sphericity of 0.95 or more
- second filler spherical filler having sphericity of 0.95 or more
- a resin composition was prepared in the same matter as in Example 1, except that about 500 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 ⁇ m, about 400 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 10 ⁇ m and about 100 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 ⁇ m were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- alumina first filler, spherical filler having sphericity of 0.95 or more
- second filler, spherical filler having sphericity of 0.95 or more having a D50 particle diameter of about 10 ⁇ m
- Comparative Examples 1 to 3 exhibit remarkably high viscosity even though the thermally conductive fillers are contained at lower ratios.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
Abstract
Description
- This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0060628 filed on May 16, 2017, the disclosure of which is incorporated herein by reference in its entirety.
- The present application relates to a resin composition.
- Since batteries, televisions, videos, computers, medical instruments, office machines or communication devices, and the like generate heat during operation and the temperature increase due to the heat causes operation failure or destruction, a heat dissipating method or a heat dissipating member used therefor has been proposed.
- For example, there is known a method in which heat is transferred to a cooling medium such as cooling water, or a temperature rise is suppressed through heat conduction to a heat sink using a metal plate having high thermal conductivity, such as aluminum or copper, and the like.
- In order to efficiently transfer heat from a heat source to the cooling medium or the heat sink, it is advantageous that the heat source and the cooling medium or the heat sink are closely contacted or thermally connected as much as possible, and to this end, a heat conductive material can be used.
- The present application relates to a resin composition. It is an object of the present application to provide a resin composition which is capable of forming a resin satisfying required physical properties such as thermal conductivity and insulation properties and has excellent handling properties such as viscosity and thixotropy.
- Among physical properties mentioned in this specification, when the measured temperature affects relevant physical properties, the physical properties are physical properties measured at room temperature, unless otherwise specified.
- In the present application, the term room temperature is a natural temperature without being heated or cooled, which may be, for example, any temperature in a range of 10° C. to 30° C., or a temperature of about 23° C. or about 25° C. or so.
- The present application relates to a resin composition. The resin composition may comprise a resin component and thermally conductive fillers.
- In one example, the resin composition may be an adhesive composition, that is, an adhesive as such, or a composition capable of forming an adhesive through a reaction such as a curing reaction. Such a resin composition may be a solvent resin composition, a water-based resin composition, or a solventless resin composition. For example, the resin composition can be prepared by adding thermally conductive fillers to be described below to a resin composition capable of forming a known acrylic adhesive, epoxy adhesive, urethane adhesive, olefin adhesive, EVA (ethylene vinyl acetate) adhesive or silicone adhesive.
- In the present application, the range of the term resin component includes components that can be converted into resins through a curing reaction or a polymerization reaction as well as components that are generally known as resins.
- In one example, as the resin component, an adhesive resin or a precursor capable of forming an adhesive resin can be applied. An example of such a resin component includes an acrylic resin, an epoxy resin, a urethane resin, an olefin resin, an EVA (ethylene vinyl acetate) resin or a silicone resin, and the like, or a precursor such as polyol or an isocyanate compound, and the like, but is not limited thereto.
- In one example, the resin composition of the present application may be a one-component resin composition or a two-component resin composition. The two-component resin composition is separated into a principal agent composition and a curing agent composition, as known in the art, and the two separated compositions are mixed and reacted to be capable of forming a resin, where when the resin composition of the present application is a two-component type, the resin composition containing the resin component and the fillers may be the principal agent composition, the curing agent composition or a mixture thereof, or may refer to a state after they have been mixed and reacted.
- In one example, the resin composition may be a urethane resin composition, and may be a two-component urethane resin composition. The term two-component urethane resin composition is a composition capable of forming a resin by blending a principal agent composition and a curing agent composition, where the polyurethane can be formed by the reaction of the principal agent and the curing agent. In one example, the resin composition of the present application may be a principal agent composition of a two-component urethane resin composition, a curing agent composition of a two-component urethane resin composition or a mixture of the principal agent and curing agent compositions, or may refer to a mixture in which the resin has been formed by the urethane reaction in the mixture.
- The principal agent composition of the two-component urethane-based resin composition may comprise at least polyol, and the curing agent composition may comprise an isocyanate compound such as polyisocyanate.
- In this case, the urethane resin, that is, the polyurethane formed by the reaction of the two-component urethane resin composition may comprise at least a polyol-derived unit and a polyisocyanate-derived unit. In this case, the polyol-derived unit may be a unit in which the polyol is formed by a urethane reaction with the polyisocyanate, and the polyisocyanate-derived unit may be a unit in which the polyisocyanate is formed by a urethane reaction with the polyol.
- In order to secure the physical properties, as the polyol at least included in the principal agent composition, a resin composition comprising polyol which is amorphous or has sufficiently low crystallinity may be applied.
- In the present application, the term amorphous means a case where a crystallization temperature (Tc) and a melting temperature (Tm) are not observed in the following DSC (differential scanning calorimetry) analysis. The DSC analysis can be performed in a range of −80° C. to 60° C. at a rate of 10° C./minute, which can be measured, for example, by a method of raising the temperature from 25° C. to 60° C. at the above rate, lowering it to −80° C. again and raising it to 60° C. again. Furthermore, the sufficiently low crystallinity herein means a case where the melting point (Tm) observed in the DSC analysis is about 20° C. or lower, about 15° C. or lower, about 10° C. or lower, about 5° C. or lower, about 0° C. or lower, about −5° C. or lower, about −10° C. or lower, or about −20° C. or lower. The lower limit of the melting point is not particularly limited, and for example, the melting point may be about −80° C. or higher, about −75° C. or higher, or about −70° C. or higher.
- As the polyol as above, an ester-based polyol to be described below can be exemplified. That is, among the ester-based polyols, a carboxylic acid-based polyol or a caprolactone-based polyol, specifically polyol having a structure to be described below, effectively satisfies the above-mentioned characteristics.
- Generally, the carboxylic acid-based polyol is formed by a urethane reaction of a component comprising dicarboxylic acid and polyol (ex. diol or triol), and the caprolactone-based polyol is formed by reacting caprolactone and polyol (ex. diol or triol), where the polyol satisfying the above-described physical properties can be constituted through control of the kind and ratio of each component.
- In one example, the polyol may be polyol represented by Formula 1 or 2 below.
- In Formulas 1 and 2, X is a dicarboxylic acid-derived unit, Y is a polyol-derived unit, for example, a triol or diol unit, and n and m are arbitrary numbers.
- Here, the dicarboxylic acid-derived unit is a unit formed by a urethane reaction of dicarboxylic acid with polyol, and the polyol-derived unit is a unit formed by a urethane reaction of polyol with dicarboxylic acid or caprolactone.
- That is, when a hydroxyl group of the polyol and a carboxyl group of the dicarboxylic acid are reacted, a water (H2O) molecule is desorbed by a condensation reaction to form an ester bond, where after the dicarboxylic acid forms the ester bond by the condensation reaction, X in Formula 1 above means a moiety excluding the ester bond moiety, and after the polyol also forms the ester bond by the condensation reaction, Y is a moiety excluding the ester bond, and the ester bond is represented in Formula 1.
- In addition, after the polyol forms an ester bond with caprolactone, Y in Formula 2 also represents a moiety excluding the ester bond.
- On the other hand, when the polyol-derived unit of Y herein is a unit derived from polyol containing three or more hydroxyl groups such as a triol unit, a structure in which the Y moiety is branched in the structure of the above formula may be realized.
- The kind of the dicarboxylic acid-derived unit of X in Formula 1 is not particularly limited, but it may be any one unit selected from the group consisting of a phthalic acid unit, an isophthalic acid unit, a terephthalic acid unit, a trimellitic acid unit, a tetrahydrophthalic acid unit, a hexahydrophthalic acid unit, a tetrachlorophthalic acid unit, an oxalic acid unit, an adipic acid unit, an azelaic acid unit, a sebacic acid unit, a succinic acid unit, a malic acid unit, a glutaric acid unit, a malonic acid unit, a pimelic acid unit, a suberic acid unit, a 2,2-dimethylsuccinic acid unit, a 3,3-dimethylglutaric acid unit, a 2,2-dimethylglutaric acid unit, a maleic acid unit, a fumaric acid unit, an itaconic acid unit and a fatty acid unit for securing units and desired physical properties, and an aliphatic dicarboxylic acid-derived unit is more advantageous than an aromatic dicarboxylic acid-derived unit in consideration of the glass transition temperature of the cured resin layer.
- In Formulas 1 and 2, the kind of the polyol-derived unit of Y is not particularly limited, but it may be any one or two or more selected from the group consisting of an ethylene glycol unit, a propylene glycol unit, an 1,2-butylene glycol unit, a 2,3-butylene glycol unit, an 1,3-propanediol unit, an 1,3-butanediol unit, an 1,4-butanediol unit, an 1,6-hexanediol unit, a neopentyl glycol unit, an 1,2-ethylhexyldiol unit, an 1,5-pentanediol unit, an 1,10-decanediol unit, an 1,3-cyclohexanedimethanol unit, an 1,4-cyclohexanedimethanol unit, a glycerin unit and a trimethylol propane unit for securing units and desired physical properties.
- In Formula 1, n is an arbitrary number, and the range may be selected in consideration of desired physical properties, and may be, for example, about 2 to 10 or 2 to 5.
- In Formula 2, m is an arbitrary number, and the range may be selected in consideration of desired physical properties, and may be, for example, about 1 to 10 or 1 to 5.
- When n and m in Formulas 1 and 2 are excessively large, the crystallinity of the polyol can be strongly expressed.
- The molecular weight of this polyol may be adjusted in consideration of desired low viscosity characteristics, durability or adhesiveness, and the like, which may be, for example, in a range of about 300 to 2,000. The molecular weight mentioned in this specification may be, for example, a weight average molecular weight measured by using GPC (gel permeation chromatograph), and unless otherwise specified herein, the molecular weight of a polymer means a weight average molecular weight.
- The kind of the polyisocyanate contained in the curing agent composition of the two-component urethane-based resin composition is not particularly limited, but it may be advantageous that it is an alicyclic series in order to secure desired physical properties. In this specification, the term polyisocyanate may mean a multifunctional isocyanate compound containing at least two isocyanate groups.
- The polyisocyanate may be an aromatic polyisocyanate compound such as tolylene diisocyanate, diphenylmethane diisocyanate, phenylenediisocyanate, polyethylenephenylene polyisocyanate, xylene diisocyanate, tetramethylxylylene diisocyanate, trizine diisocyanate, naphthalene diisocyanate and triphenylmethane triisocyanate, an aliphatic polyisocyanate such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate methyl, ethylene diisocyanate, propylene diisocyanate or tetramethylene diisocyanate, or an alicyclic polyisocyanate such as transcyclohexane-1,4-diisocyanate, isoboron diisocyanate, bis(isocyanate methyl)cyclohexane diisocyanate or dicyclohexylmethane diisocyanate, and the like, a carbodiimide-modified polyisocyanate or an isocyanurate-modified polyisocyanate of any one or two or more of the foregoing, and the like can be used, but the application of polyisocyanates other than aromatics is appropriate.
- The ratio of the polyol to the polyisocyanate in the resin composition is not particularly limited and is appropriately controlled so as to enable the urethane reaction thereof.
- The resin composition may comprise fillers together with the resin component. The fillers may be thermally conductive fillers. The term thermally conductive filler means a material known to have thermal conductivity of about 0.5 W/mK or more, about 1 W/mK or more, 1.5 W/mK or more, 2 W/mK or more, 2.5 W/mK or more, 3 W/mK or more, 4 W/mK or more, 4.5 W/mK or more, about 5 W/mK or more, 5.5 W/mK or more, 6 W/mK or more, 6.5 W/mK or more, 7 W/mK or more, 7.5 W/mK or more, 8 W/mK or more, 8.5 W/mK or more, 9 W/mK or more, 9.5 W/mK or more, 10 W/mK or more, 10.5 W/mK or more, 11 W/mK or more, 11.5 W/mK or more, 12 W/mK or more, 12.5 W/mK or more, 13 W/mK or more, 13.5 W/mK or more, 14 W/mK or more, 14.5 W/mK or more, or about 15 W/mK or more. In one example, the thermal conductivity of the thermally conductive filler may be about 400 W/mK or less, about 350 W/mK or less, about 300 W/mK or less, about 250 W/mK or less, about 200 W/mK or less, about 150 W/mK or less, about 100 W/mK or less, about 90 W/mK or less, about 80 W/mK or less, about 70 W/mK or less, about 60 W/mK or less, about 50 W/mK or less, about 40 W/mK or less, about 30 W/mK or less, about 20 W/mK or less, or about 15 W/mK or less or so. The kind of thermally conductive fillers is not particularly limited, but ceramic fillers can be applied in consideration of insulation and the like. For example, ceramic particles such as alumina, AlN (aluminum nitride), BN (boron nitride), silicon nitride, SiC or BeO may be used. If insulation properties can be secured, application of carbon fillers such as graphite may also be considered.
- The resin composition may comprise the thermally conductive fillers in an amount of about 600 parts by weight or more relative to 100 parts by weight of the resin component. In another example, the ratio of the fillers may be 650 parts by weight or more, or 700 parts by weight or more, relative to 100 parts by weight of the resin component. The ratio may be about 2,000 parts by weight or less, about 1,500 parts by weight or less, or about 1,100 parts by weight or less, relative to 100 parts by weight of the resin component. It is possible to secure desired physical properties such as thermal conductivity and insulation within the ratio range of the fillers.
- When the resin composition is a principal agent composition or a curing agent composition of a two-component resin composition, the ratio of the fillers in the resin composition mentioned in this specification may be a ratio of the resin component that is a principal agent of the principal agent composition, or a ratio of the curing agent that is a resin component of the curing agent composition, or may be a ratio of the final resin formed by the reaction of the principal agent and the curing agent.
- If the excessive amount of the fillers is applied for securing the thermal conductivity and the insulation as above, the viscosity of the resin composition is greatly increased and the handling property is accordingly deteriorated, and even after the resin material is formed, it contains bubbles or voids, whereby the thermal conductivity may be lowered.
- Accordingly, in the resin composition, at least three kinds of fillers having different particle diameters are applied at a predetermined ratio.
- For example, the resin composition may comprise a first thermally conductive filler having a D50 particle diameter of 35 μm or more, a second thermally conductive filler having a D50 particle diameter in a range of 15 μm to 30 μm, and a third thermally conductive filler having a D50 particle diameter of 1 to 4 μm.
- Here, the D50 particle diameter is a particle diameter (median diameter) at 50% of accumulation of particle size distribution on a volumetric basis, which means a particle diameter at the point where the cumulative value becomes 50% in the cumulative curve that the particle size distribution is obtained on a volumetric basis and the whole volume is set to 100%. Such a D50 particle diameter can be measured by a laser diffraction method.
- In one example, the D50 particle diameter of the first thermally conductive filler may be in a range of 35 to 80 μm or in a range of about 40 to 70 μm. Also, the D50 particle diameter of the second thermally conductive filler may be in a range of 15 to 25 μm or in a range of about 20 to 25 μm. Furthermore, the D50 particle diameter of the third thermally conductive filler may be in a range of 1 to 3 μm or in a range of about 2 to 3 μm.
- The relationship of the D50 particle diameters in the respective thermally conductive fillers may be controlled, and for example, a ratio (A/B) of the D50 particle diameter (A) of the first thermally conductive filler to the D50 particle diameter (B) of the second thermally conductive filler may be in a range of 1.5 to 10, and a ratio (B/C) of the D50 particle diameter (B) of the second thermally conductive filler to the D50 particle diameter (C) of the third thermally conductive filler may be in a range of 8 to 15.
- In another example, the ratio (A/B) may be 2 or more, and may be 9 or less, 8 or less, 7 or less, 6 or less, or 5 or less. In another example, the ratio (B/C) may be 9 or more, or 10 or more, and may be 14 or less, 13 or less, or 12 or less.
- The resin composition may comprise 30 to 50 wt % or about 35 to 45 wt % of the first thermally conductive filler, and 25 to 45 wt %, about 25 to 40 wt % or about 30 to 45 wt % of the second thermally conductive filler, and may comprise 15 to 35 wt % or about 20 to 30 wt % of the third thermally conductive filler, when the total weight of the first to third thermally conductive fillers is 100 wt %.
- By applying three kinds of fillers having the particle diameters in the ratios, it is possible to provide a resin composition in which the handling property is secured by exhibiting appropriate viscosity even when an excessive amount of fillers is applied.
- The shape of the filler is not particularly limited, which may be selected in consideration of the viscosity and thixotropy of the resin composition, the settling possibility in the composition, desired thermal resistance or thermal conductivity, insulation, a filling effect or dispersibility, and the like. For example, it is advantageous to use a spherical filler in consideration of the amount to be filled, but in consideration of formation of a network, conductivity, thixotropy, etc., a non-spherical filler, for example, a filler having a shape such as a needle shape or a plate shape can also be used.
- In the present application, the term spherical particle means a particle having sphericity of about 0.95 or more, and the non-spherical particle means a particle having sphericity of less than 0.95. The sphericity can be confirmed through particle shape analysis of particles, which can be measured by the method described in the examples to be described below.
- In one example, all the spherical fillers, that is, fillers having sphericity of 0.95 or more may be used as the first to third thermally conductive fillers in consideration of the filling effect as described above. In another example, at least one of the first to third thermally conductive fillers may be a non-spherical filler having sphericity of less than 0.95. For example, when spherical fillers are used as the first and second thermally conductive fillers and non-spherical particles are used as the third thermally conductive filler, the composition may exhibit thixotropy.
- The resin composition may basically comprise the above components, that is, the resin component and the thermally conductive fillers, and may also comprise other components, if necessary. For example, the resin composition may further comprise a viscosity control agent, such as a thixotropic agent, a diluent, a dispersing agent, a surface treatment agent or a coupling agent, for controlling viscosity, for example, for increasing or decreasing viscosity, or for controlling viscosity according to shear force.
- The thixotropic agent can control the viscosity of the resin composition according to shear force, so that a process of manufacturing a battery module can be effectively performed. The usable thixotropic agent can be exemplified by fumed silica and the like.
- The diluent or dispersing agent is usually used for lowering the viscosity of the resin composition, and as long as it can exhibit the above action, a variety of shapes known in the art can be used without limitation.
- The surface treatment agent is used for surface treatment of the filler introduced into the resin composition, and as long as it can exhibit the above action, a variety of shapes known in the art can be used without limitation.
- The coupling agent may be used, for example, to improve the dispersibility of the thermally conductive fillers such as alumina, and as long as it can exhibit the above action, a variety of shapes known in the art can be used without limitation.
- The resin composition may further comprise a flame retardant or a flame retardant aid. Such a resin composition can form a flame retardant resin composition. As the flame retardant, various known flame retardants can be applied without particular limitation, and for example, solid phase filler-type flame retardants or liquid flame retardants and the like can be applied. The flame retardant includes an organic flame retardant such as melamine cyanurate or an inorganic flame retardant such as magnesium hydroxide, but is not limited thereto.
- When the amount of the filler filled in the resin composition is large, a liquid type flame retardant material (TEP, triethyl phosphate or TCPP, tris(1,3-chloro-2-propyl)phosphate, etc.) may also be used. Furthermore, a silane coupling agent capable of acting as a flame retardant synergist may also be added.
- The resin composition may comprise any one or two or more of the above components.
- Such a resin composition can form a resin having excellent thermal conductivity and satisfying other required physical properties such as insulation.
- For example, the resin composition may have thermal conductivity of about 2 W/mK or more, 2.5 W/mK or more, 3 W/mK or more, 3.5 W/mK or more, or 4 W/mK or more, or may form such a resin. The thermal conductivity may be 50 W/mK or less, 45 W/mK or less, 40 W/mK or less, 35 W/mK or less, 30 W/mK or less, 25 W/mK or less, 20 W/mK or less, 15 W/mK or less, 10 W/mK or less, 5 W/mK or less, 4.5 W/mK or less, or about 4.0 W/mK or less. The thermal conductivity may be, for example, a numerical value measured according to ASTM D5470 standard or ISO 22007-2 standard. The thermal conductivity can be secured by controlling the kind of the resin components used in the resin composition and the ratios of the thermally conductive fillers as described above, and the like. For example, among resin components known to be generally usable as adhesives, it is known that an acrylic resin, a urethane resin and a silicone resin have similar heat conduction properties to each other, an epoxy resin has excellent thermal conductivity relative to these resins, and an olefin resin has higher thermal conductivity than the epoxy resin. Therefore, it is possible to select one having excellent thermal conductivity among the resins as necessary. However, in general, the desired thermal conductivity cannot be secured with only the resin component, so that the thermal conductivity can be achieved by incorporating the filler component into the resin layer at a proper ratio.
- The resin composition may be an adhesive material, as described above, and may have adhesive force of about 50 gf/10 mm or more, about 70 gf/10 mm or more, about 80 gf/10 mm or more, or about 90 gf/10 mm or more, and about 1,000 gf/10 mm or less, about 950 gf/10 mm or less, about 900 gf/10 mm or less, about 850 gf/10 mm or less, about 800 gf/10 mm or less, about 750 gf/10 mm or less, about 700 gf/10 mm or less, about 650 gf/10 mm or less, or about 600 gf/10 mm or less, or may form a resin layer having this adhesive force. The adhesive force may be a value measured at a peeling speed of about 300 mm/min and a peeling angle of 180 degrees. Furthermore, the adhesive force may be an adhesive force to aluminum.
- The resin composition is an electrically insulating resin composition, which may have an insulation breakdown voltage of about 3 kV/mm or more, about 5 kV/mm or more, about 7 kV/mm or more, 10 kV/mm or more, 15 kV/mm or more, or 20 kV/mm or more, as measured based on ASTM D149, or may form such a resin layer. The higher the value of the insulation breakdown voltage is, it exhibits more excellent insulating properties, and thus the insulation breakdown voltage is not particularly limited, but it may be about 50 kV/mm or less, 45 kV/mm or less, 40 kV/mm or less, 35 kV/mm or less, or 30 kV/mm or less, considering compositions or the like. Such an insulation breakdown voltage can also be controlled by controlling the insulation of the resin component or the type of the filler, and the like. In general, among the thermally conductive fillers, the ceramic filler is known as a component that can secure insulation.
- The resin composition may be a flame retardant resin composition. The term flame retardant resin composition may mean a resin composition showing a V-0 rating in UL 94 V Test (vertical burning test) or a resin composition capable of forming such a resin.
- It may be advantageous that the resin composition also has a low shrinkage ratio during curing or after curing. Through this, it is possible to prevent the occurrence of peeling or voids, and the like that may occur during manufacturing or use processes. The shrinkage ratio can be appropriately adjusted within a range capable of exhibiting the above-described effect, which may be, for example, less than 5%, less than 3%, or less than about 1%. The lower the value of the shrinkage ratio is, the more advantageous it is, and thus the lower limit is not particularly limited.
- It may be advantageous that the resin composition also has a low coefficient of thermal expansion (CTE). Through this, it is possible to prevent the occurrence of peeling or voids, and the like that may occur during manufacturing or use processes. The coefficient of thermal expansion can be appropriately adjusted within a range capable of exhibiting the above-described effect, which may be, for example, less than 300 ppm/K, less than 250 ppm/K, less than 200 ppm/K, less than 150 ppm/K, or less than about 100 ppm/K. The lower the value of the coefficient of thermal expansion is, the more advantageous it is, and thus the lower limit is not particularly limited.
- The resin composition may also exhibit an appropriate viscosity by comprising the above components. In one example, the resin composition may have a viscosity at room temperature (frequency: 10 Hz) in a range of 50 Pas to 500 Pas.
- Such a resin composition may exhibit excellent physical properties such as excellent handling properties, processability and high thermal conductivity, thereby being used effectively as a heat dissipation material or a heat conduction material in various devices or instruments, and the like, including batteries, televisions, videos, computers, medical instruments, office machines or communication devices, and the like.
- The present application can provide a thermally conductive resin composition exhibiting high thermal conductivity while having excellent handling properties. The thermally conductive resin composition can be kept excellent in all other physical properties such as insulation.
- Hereinafter, the transmittance-variable device of the present application will be described in detail by way of examples and comparative examples, but the scope of the present application is not limited by the following transmittance-variable device.
- 1. Evaluation of Thermal Conductivity
- The thermal conductivity of the resin composition was measured according to ASTM D5470 standard. After a resin layer formed using a resin composition was placed between two copper bars, one of the two copper bars was brought into contact with a heater and the other was brought into contact with a cooler, and then a thermal equilibrium state (a state of showing a temperature change of about 0.1° C. or less for 5 minutes) was made by adjusting the capacity of the cooler while keeping the heater at a constant temperature, according to ASTM D5470 standard.
- The temperature of each copper bar was measured in the thermal equilibrium state, and the thermal conductivity (K, unit: W/mK) was evaluated according to the following equation. Upon evaluating the thermal conductivity, the pressure applied to the resin layer was adjusted to be about 11 Kg/25 cm2, and when the thickness of the resin layer was changed during the measurement, the thermal conductivity was calculated based on the final thickness.
-
K=(QXdx)/(AXdT) <Thermal Conductivity Equation> - In Equation above, K is thermal conductivity (W/mK), Q is heat (unit: W) transferred per unit time, dx is the thickness of the resin layer (unit: m), A is the cross-sectional area (unit: m2) of the resin layer, and dT is the temperature difference (unit: K) between the copper bars.
- 3. D50 Particle Diameter of Filler
- The D50 particle diameter of the filler was measured with a MASTERSIZER3000 instrument from Marvern Inc., based on ISO-13320 standard. Ethanol was used as a solvent upon the measurement. The incident laser is scattered by the particles dispersed in the solvent, and the intensity and the directional value of the scattered laser vary depending on the size of the particles, which are analyzed using the Mie theory. Through the above analysis, the particle diameter can be evaluated by obtaining the distribution through conversion to the diameter of a sphere having the same volume as that of the dispersed particle and obtaining the D50 value as the median value of the distribution through that.
- 4. Evaluation of Sphericity of Filler
- The sphericity of the filler as a three-dimensional particle is defined as the ratio (S′/S) of the surface area (S′) of the sphere having the same volume as the particle to the surface area (S) of the particle, which is usually an average value of circularity for the actual particles.
- The circularity is a ratio of a boundary of a circle having the same area (A) as the image obtained from the two-dimensional image of the particle to the boundary (P) of the image, theoretically being obtained by the following equation and a value from 0 to 1, and the circularity is 1 for an ideal circle.
-
Circularity=4πA/P 2 <Circularity Equation> - In this specification, the sphericity value is an average value of the circularity measured by a particle shape analysis instrument (FPIA-3000) from Marvern Inc.
- 5. Viscosity of Resin Composition
- The viscosity of the resin composition was measured in a frequency sweep mode at 25° C. for the section from 0.1 to 100 Hz, after equipping an ARES-G2 instrument from TA Company with 8 mm parallel plates and then positioning the composition between the plates so as not to flow down, and the values at 10 Hz were described in Table 1.
- As a resin composition, a two-component urethane-based adhesive composition was prepared. A principal agent composition comprising, as a caprolactone-based polyol of Formula A below, the polyol having m of Formula A below, as a number of repeated units, in a range of about 1 to 3 and containing an ethylene glycol and propylene glycol-derived unit as Y of Formula A below being a polyol-derived unit, was used as a principal agent composition, and a composition comprising polyisocyanate (HDI, hexamethylene diisocyanate) was used as a curing agent composition. Alumina was compounded to the resin composition so as to be capable of exhibiting thermal conductivity. The alumina was compounded to each of the principal agent composition and the curing agent composition by bisecting about 1,000 parts by weight of alumina by the same amount relative to 100 parts by weight of the polyurethane formed after the curing of the two-component urethane-based adhesive composition. As the alumina, alumina (first filler) having a D50 particle diameter of about 40 μm, alumina (second filler) having a D50 particle diameter of about 20 μm and alumina (third filler) having a D50 particle diameter of about 2 μm were used, and about 400 parts by weight of the first filler, about 300 parts by weight of the second filler and about 300 parts by weight of the third filler were applied, relative to 100 parts by weight of the polyurethane. As the first to third fillers, all spherical fillers having a sphericity of 0.95 or more were used. The resin composition was prepared by adjusting equivalent amounts of the principal agent composition and the curing agent composition of the two-component composition and compounding them.
- A resin composition was prepared in the same matter as in Example 1, except that about 400 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 70 μm, about 300 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 μm and about 300 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- A resin composition was prepared in the same matter as in Example 1, except that about 400 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 μm, about 400 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 μm and about 200 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- A resin composition was prepared in the same matter as in Example 1, except that about 350 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 μm, about 350 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 μm and about 300 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- A resin composition was prepared in the same matter as in Example 1, except that about 450 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 μm, about 350 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 μm and about 200 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- A resin composition was prepared in the same matter as in Example 1, except that about 400 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 μm, about 300 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 μm and about 300 parts by weight of alumina (third filler, non-spherical filler having sphericity of less than 0.95) having a D50 particle diameter of about 2 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- A resin composition was prepared in the same matter as in Example 1, except that about 400 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 70 μm, about 300 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 μm and about 300 parts by weight of alumina (third filler, non-spherical filler having sphericity of less than 0.95) having a D50 particle diameter of about 2 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- A resin composition was prepared in the same matter as in Example 1, except that about 630 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 μm and about 270 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- A resin composition was prepared in the same matter as in Example 1, except that about 630 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 μm and about 270 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- A resin composition was prepared in the same matter as in Example 1, except that about 630 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 μm and about 270 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- A resin composition was prepared in the same matter as in Example 1, except that about 400 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 μm, about 300 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 5 μm and about 300 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- A resin composition was prepared in the same matter as in Example 1, except that about 400 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 μm, about 300 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 10 μm and about 300 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- A resin composition was prepared in the same matter as in Example 1, except that about 400 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 μm, about 300 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 μm and about 300 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 5 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- A resin composition was prepared in the same matter as in Example 1, except that about 400 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 μm, about 300 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 μm and about 300 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 0.5 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- A resin composition was prepared in the same matter as in Example 1, except that about 300 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 μm, about 300 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 μm and about 300 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- A resin composition was prepared in the same matter as in Example 1, except that about 300 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 μm, about 500 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 μm and about 200 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- A resin composition was prepared in the same matter as in Example 1, except that about 500 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 40 μm, about 200 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 μm and about 300 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- A resin composition was prepared in the same matter as in Example 1, except that about 500 parts by weight of alumina (first filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 20 μm, about 400 parts by weight of alumina (second filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 10 μm and about 100 parts by weight of alumina (third filler, spherical filler having sphericity of 0.95 or more) having a D50 particle diameter of about 2 μm were used as the thermally conductive fillers, relative to 100 parts by weight of the polyurethane.
- The thermal conductivity and viscosity determined for Examples and Comparative Examples above were summarized and described in Table 1 below.
-
TABLE 1 Thermal Conductivity Viscosity (unit: W/mK) (unit: Pa · s) Example 1 3.0 59.7 2 3.1 61.3 3 3.0 68.7 4 3.0 71.9 5 3.0 63.5 6 3.1 80 7 3.1 75 Comparative 1 2.6 351 Example 2 2.5 298 3 2.4 345 4 2.8 103.8 5 2.8 121.1 6 2.8 110.8 7 2.7 195.5 8 2.6 143.9 9 2.7 140.3 10 2.8 122.4 11 2.8 120.6 - From the results of Table 1, it can be seen that the composition having low viscosity is obtained even when an excessive amount of fillers is introduced to secure high thermal conductivity.
- For example, from the results of Examples and Comparative Examples 1 to 3, it can be confirmed that Comparative Examples 1 to 3 exhibit remarkably high viscosity even though the thermally conductive fillers are contained at lower ratios.
- Also, comparing Examples and Comparative Examples 4 to 7, it can be confirmed that even when three kinds of thermally conductive fillers are applied in the same manner, the results are significantly different depending on the D50 particle diameter of each filler, and it can be confirmed from the results of Comparative Examples 8 to 11 that there is also a large difference in the results depending on the ratios of the three kinds of particles and the like.
- Furthermore, in the case of Examples 6 and 7, it was confirmed that while the shapes of the fillers changed, the resin composition exhibited thixotropy.
Claims (15)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020170060628A KR102166470B1 (en) | 2017-05-16 | 2017-05-16 | Resin Composition |
KR10-2017-0060628 | 2017-05-16 | ||
PCT/KR2018/005544 WO2018212553A1 (en) | 2017-05-16 | 2018-05-15 | Resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
US20190309207A1 true US20190309207A1 (en) | 2019-10-10 |
US10988656B2 US10988656B2 (en) | 2021-04-27 |
Family
ID=64274384
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/470,415 Active 2038-07-03 US10988656B2 (en) | 2017-05-16 | 2018-05-15 | Resin composition |
Country Status (6)
Country | Link |
---|---|
US (1) | US10988656B2 (en) |
EP (1) | EP3626770B1 (en) |
JP (1) | JP6956789B2 (en) |
KR (1) | KR102166470B1 (en) |
CN (1) | CN110023388B (en) |
WO (1) | WO2018212553A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111621139A (en) * | 2020-06-29 | 2020-09-04 | 江西伟普科技有限公司 | Wave-absorbing heat-conducting flexible composite material and preparation method thereof |
EP4118162A4 (en) * | 2020-03-13 | 2023-11-29 | DDP Specialty Electronic Materials US, LLC | Thermal interface material comprising magnesium hydroxide |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102070573B1 (en) | 2018-04-20 | 2020-01-29 | 주식회사 엘지화학 | Resin composition and battery module comprising the same |
KR102382554B1 (en) * | 2019-03-27 | 2022-04-04 | 주식회사 엘지화학 | Resin Composition |
KR102421433B1 (en) * | 2019-04-08 | 2022-07-18 | 주식회사 엘지화학 | Curable Resin Composition |
JP7357995B2 (en) * | 2019-08-19 | 2023-10-10 | エルジー・ケム・リミテッド | resin composition |
KR102393127B1 (en) * | 2019-08-19 | 2022-05-02 | 주식회사 엘지화학 | Resin Composition |
CN115135709B (en) * | 2020-03-05 | 2024-03-08 | 陶氏环球技术有限责任公司 | Shear thinning thermally conductive silicone composition |
JP7198398B1 (en) | 2021-11-10 | 2023-01-04 | 東洋インキScホールディングス株式会社 | Surface-treated inorganic particles, inorganic particle-containing composition, thermally conductive cured product, structure and laminate |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5828835B2 (en) | 1973-12-05 | 1983-06-18 | フロマツチヤ− インコ−ポレ−テツド | Kairiyouekitaiikoseigiyosouchi |
JPS5261000A (en) * | 1975-11-15 | 1977-05-19 | Hinomoto Denki Kk | Heattconductive insulating material |
JPS5511932A (en) | 1978-07-11 | 1980-01-28 | Boeicho Gijutsu Kenkyu Honbuch | Canard |
JP3924865B2 (en) * | 1997-09-19 | 2007-06-06 | 株式会社安川電機 | Epoxy resin composition |
US6610635B2 (en) | 2000-09-14 | 2003-08-26 | Aos Thermal Compounds | Dry thermal interface material |
KR100858836B1 (en) | 2001-05-14 | 2008-09-17 | 다우 코닝 도레이 캄파니 리미티드 | Heat-conductive silicone composition |
JP2004346094A (en) * | 2003-05-16 | 2004-12-09 | Daicel Chem Ind Ltd | Polyurethane resin and surface film layer of synthetic leather obtained using the same |
US7170038B2 (en) * | 2004-04-27 | 2007-01-30 | Premix Inc. | Molding compounds for use in induction heating applications and heating elements molded from these compounds |
JP5305656B2 (en) | 2004-08-23 | 2013-10-02 | モーメンティブ・パフォーマンス・マテリアルズ・インク | Thermally conductive composition and method for producing the same |
EP1975188A1 (en) * | 2007-03-27 | 2008-10-01 | Sika Technology AG | Cycloaliphatic polyurethane compound containing cycloaliphatic dialdimines |
JP5155033B2 (en) | 2008-06-26 | 2013-02-27 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Thermally conductive silicone composition |
US8182405B2 (en) * | 2008-09-30 | 2012-05-22 | Canon Kabushiki Kaisha | Developing roller, developing roller production method, process cartridge, and electrophotographic apparatus |
JP2011040565A (en) * | 2009-08-11 | 2011-02-24 | Fuji Electric Systems Co Ltd | Thermal conductive sheet, semiconductor device using the same, and method of manufacturing the same |
WO2011125636A1 (en) | 2010-04-08 | 2011-10-13 | 電気化学工業株式会社 | Thermally conductive moisture curable resin composition |
JP5761639B2 (en) | 2010-09-30 | 2015-08-12 | 日本発條株式会社 | Adhesive resin composition, cured product thereof, and adhesive film |
JP5664563B2 (en) | 2012-01-23 | 2015-02-04 | 信越化学工業株式会社 | Thermally conductive silicone composition and cured product thereof |
US20150065613A1 (en) * | 2012-04-26 | 2015-03-05 | Dow Mf Produktions Gmbh & Co. Ohg | Epoxy adhesive composition |
DE102012109500A1 (en) * | 2012-10-05 | 2014-04-10 | Dr. Neidlinger Holding Gmbh | Heat-dissipating polymer and resin compositions for producing the same |
JP6414799B2 (en) * | 2013-01-15 | 2018-10-31 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, laminate, metal foil clad laminate and printed wiring board |
JP6040261B2 (en) * | 2013-02-08 | 2016-12-07 | 昭和電工株式会社 | Thermally conductive adhesive composition, thermally conductive adhesive sheet, flame retardant thermally conductive adhesive composition, flame retardant thermally conductive adhesive sheet, thermally conductive insulating coating and metal molded product |
CN103194062B (en) * | 2013-03-29 | 2015-05-27 | 株洲时代电气绝缘有限责任公司 | Polyimide film and preparation method thereof |
US9745411B2 (en) | 2013-06-27 | 2017-08-29 | Hitachi Chemical Company, Ltd. | Resin composition, resin sheet, cured resin sheet, resin sheet structure, cured resin sheet structure, method for producing cured resin sheet structure, semiconductor device, and LED device |
EP2878619A1 (en) * | 2013-12-02 | 2015-06-03 | LANXESS Deutschland GmbH | Polyester compositions |
US9353245B2 (en) * | 2014-08-18 | 2016-05-31 | 3M Innovative Properties Company | Thermally conductive clay |
KR102544343B1 (en) * | 2015-05-22 | 2023-06-19 | 모멘티브 파포만스 마테리아루즈 쟈판 고도가이샤 | thermally conductive composition |
KR101793948B1 (en) | 2015-11-24 | 2017-11-08 | 강토중공업 (주) | Safety Lock Type Quick Coupler |
KR102146540B1 (en) * | 2017-09-15 | 2020-08-20 | 주식회사 엘지화학 | Battery module |
-
2017
- 2017-05-16 KR KR1020170060628A patent/KR102166470B1/en active IP Right Grant
-
2018
- 2018-05-15 CN CN201880004581.2A patent/CN110023388B/en active Active
- 2018-05-15 EP EP18802691.8A patent/EP3626770B1/en active Active
- 2018-05-15 WO PCT/KR2018/005544 patent/WO2018212553A1/en unknown
- 2018-05-15 US US16/470,415 patent/US10988656B2/en active Active
- 2018-05-15 JP JP2019529842A patent/JP6956789B2/en active Active
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4118162A4 (en) * | 2020-03-13 | 2023-11-29 | DDP Specialty Electronic Materials US, LLC | Thermal interface material comprising magnesium hydroxide |
CN111621139A (en) * | 2020-06-29 | 2020-09-04 | 江西伟普科技有限公司 | Wave-absorbing heat-conducting flexible composite material and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
US10988656B2 (en) | 2021-04-27 |
CN110023388A (en) | 2019-07-16 |
JP2020500982A (en) | 2020-01-16 |
KR102166470B1 (en) | 2020-10-16 |
KR20180125824A (en) | 2018-11-26 |
JP6956789B2 (en) | 2021-11-02 |
CN110023388B (en) | 2021-08-17 |
WO2018212553A1 (en) | 2018-11-22 |
EP3626770B1 (en) | 2022-02-09 |
EP3626770A1 (en) | 2020-03-25 |
EP3626770A4 (en) | 2020-05-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10988656B2 (en) | Resin composition | |
JPWO2012157627A1 (en) | Curable heat dissipation composition | |
KR102513841B1 (en) | Resin Composition | |
KR102421433B1 (en) | Curable Resin Composition | |
KR102477380B1 (en) | Method of Manufacturing Battery Module and Manufacturing Device of Battery Module | |
KR102393127B1 (en) | Resin Composition | |
KR102112790B1 (en) | Resin Composition | |
KR102248921B1 (en) | A composition and method for preparing the same | |
KR102535889B1 (en) | cureable composition | |
TWI832151B (en) | Composition and battery comprising thereof | |
KR102214563B1 (en) | Resin Composition | |
KR102406556B1 (en) | Injection Device of Resin Composition | |
KR20220043766A (en) | resin composition | |
TW202239804A (en) | Curable composition, two-component curable composition and device including the same | |
KR20220115222A (en) | Composition and method for preparing the composition | |
CN116568722A (en) | Curable composition | |
KR20230164383A (en) | Curable composition | |
KR20210026417A (en) | Method for evaluating flowability of resin composition in equipment |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FEPP | Fee payment procedure |
Free format text: ENTITY STATUS SET TO UNDISCOUNTED (ORIGINAL EVENT CODE: BIG.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
AS | Assignment |
Owner name: LG CHEM, LTD., KOREA, REPUBLIC OF Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KANG, SEONG KYUN;CHO, YOON GYUNG;KANG, YANG GU;AND OTHERS;REEL/FRAME:049503/0484 Effective date: 20190514 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: PUBLICATIONS -- ISSUE FEE PAYMENT RECEIVED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: PUBLICATIONS -- ISSUE FEE PAYMENT VERIFIED |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |